JP6929333B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

The present invention relates to a water-in-oil emulsified cosmetic.

In recent years, sunscreen cosmetics tend to contain a large amount of ultraviolet scattering agents and ultraviolet absorbers in order to obtain a high SPF (Sun Protection Factor) effect. Techniques for sunscreen cosmetics containing them are disclosed (for example, Patent Document 1 and Patent Document 2).
As the ultraviolet scattering agent, metal oxides such as titanium oxide, zinc oxide and cerium oxide are preferably used. These UV scatterers are excellent in that they shield not only UVB but also UVA and do not irritate the skin. For this reason, sunscreen cosmetics that realize a high SPF effect only with an ultraviolet scattering agent without adding an ultraviolet absorber that may cause skin irritation are also commercially available.
In sunscreen cosmetics with low skin irritation, there is a design requirement to reduce the amount of UV absorbers and to add as much metal oxide as possible. However, if the amount of the metal oxide is increased, problems such as heavy elongation when applied to the skin and whiteness remaining on the skin (decreased transparency) may occur. Furthermore, it has been regarded as a problem that it becomes white when it gets wet with water.
Under these circumstances, various technical proposals have been made. For example, in order to improve the whiteness (low transparency) after coating, a technique for finely dividing a metal oxide to improve the transparency of visible light (Patent Document 3), and a finely divided metal oxide on the surface. A technique for processing to improve dispersibility (Patent Document 4) is known.
When the finely divided metal oxide is hydrophobized, the whiteness is not noticeable on the skin and it is difficult to turn white when wet with water, but there is a problem that the metal oxide cannot be sufficiently removed even after washing the face and remains on the skin. Rubbing the skin hard to eliminate skin residue puts a strain on the skin. Therefore, in recent years, the ease of removing cosmetics has also been emphasized in product design. Technical proposals have been made to solve this. For example, by blending N-lauroyl L glutamate di (phytosteryl, 2-octyldodecyl), the poor usability due to the large amount of UV scatterer powder and the poor cleanability due to the UV scatterer powder were improved. Water-in-oil emulsified sunscreen cosmetics have been proposed (Patent Document 5). However, using this technique is not sufficient.

Japanese Unexamined Patent Publication No. 10-120543 Special Table 2002-521417 Japanese Unexamined Patent Publication No. 9-175821 Japanese Patent No. 3567335 Japanese Patent No. 5361809

An object of the present invention is to provide a water-in-oil emulsified cosmetic that does not appear white when applied to the skin (highly transparent), does not whiten when wet with water, and is easy to wash.

The present inventor presents di (caprylic acid / capric acid) propanediol and bis- (glyceryl / lauryl) glyceryl lauryl dimethicone and / or polyglyceryl-3 polydimethyl in a water-in-oil emulsified composition containing a large amount of metal oxide. The composition containing siloxyethyldimethicone does not appear white when applied to the skin (it is transparent) and has a good usability, and when it gets wet with water, it does not turn white and is easy to wash. We have found that it is an emulsified cosmetic and completed the present invention.

The main configuration of the present invention is as follows.
(1) (A) metal oxide, (B) di (caprylic acid / capric acid) propanediol in an amount of 4 to 8% by mass per cosmetic , (C) a surfactant, and (C) a surfactant. Is a water-in-oil emulsified cosmetic containing 1 to 6% by mass of bis- (glyceryl / lauryl) glyceryl lauryl dimethicone and / or polyglyceryl-3 polydimethylsiloxyethyl dimethicone per cosmetic.
(2) The water-in-oil emulsified cosmetic according to (1), wherein the metal oxide is one or more selected from titanium oxide and zinc oxide.
(3) The water-in-oil emulsified cosmetic according to (1) or (2), which contains 18 to 30% by mass of (A) metal oxide.
(4) The water-in-oil emulsified cosmetic according to any one of (1) to (3 ), which is used for sunscreens, makeup bases, and foundations.

Despite the high content of metal oxides, the water-in-oil emulsified cosmetic of the present invention spreads well, does not cause whitening when applied to the skin, and does not turn white when wet with water. Easy to clean.

The components of the present invention will be described below.
<(A) Metal oxide>
The metal oxide used in the present invention is blended for the purpose of scattering or shielding ultraviolet rays. It is preferable to use fine particles, and examples thereof include fine particle titanium oxide and fine particle zinc oxide. Those that have been surface-treated (coated) with fatty acids, silicones, etc. may be used, and those that have been surface-treated (coated) with silicone are particularly preferable.
As these metal oxides, a simple substance may be obtained and used, or a paste-like commercially available product in which the metal oxide is stably converted into low-order particles in a volatile silicone base material may be used. As commercially available paste-like products, Cosmetic Serve WP-40TSF manufactured by Dainippon Kasei Co., Ltd., LZ-021 and LZ-F02 manufactured by TAYCA Corporation can be obtained and used. Cosmeserve WP-40TSF consists of titanium oxide, silica, aluminum hydroxide, (dimethicone / methicone) copolymer, PEG-9 polydimethylsiloxyethyl dimethicone, and cyclopentasiloxane. LZ-021 manufactured by Teika Co., Ltd. is composed of zinc oxide, hydrogen dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, cyclopentasiloxane, and tocopherol. LZ-F02 manufactured by TAYCA CORPORATION consists of zinc oxide, cyclopentasiloxane, PEG-9 dimethicone, dimethicone, and tocopherol. The amount of the metal oxide to be blended is appropriately determined depending on the intended purpose, but in order to obtain a high SPF, it is preferably blended in an amount of 18 to 30% by mass, more preferably 20 to 30% by mass. In order to obtain a sunscreen cosmetic having approximately SPF 50+ and PA ++++, it is preferable to add 20 to 30% by mass of a metal oxide.

<(B) Di (caprylic acid / capric acid) propanediol>
The di (caprylic acid / capric acid) propanediol used in the present invention is a diester of 1,3-propanediol and a mixed fatty acid composed of caprylic acid and capric acid. This is a colorless to pale yellow ester oil. As a commercially available product, Saracos PR-85 manufactured by Nisshin Oillio Co., Ltd. can be obtained and used. In the present invention, it is preferable to add 1 to 15% by mass, more preferably 4 to 8% by mass of di (caprylic acid / capric acid) propanediol.

<(C) Surfactant>
The cosmetic of the present invention is a water-in-oil emulsified cosmetic. In the present invention, in order to obtain the effect of the present invention (the effect of not whitening when wet with water and being easy to wash), (B) di (caprylic acid / capric acid) is separated from the surfactant required for emulsification. ) It is essential to contain bis- (glyceryl / lauryl) glyceryl lauryl dimethicone and / or polyglyceryl-3 polydimethylsiloxyethyl dimethicone along with propanediol.
(Bis- (glyceryl / lauryl) glyceryl lauryl dimethicone)
It is a silicone emulsifier. Examples of commercially available products include (trade name: ABIL EM120) manufactured by EVONIK.
(Polyglyceryl-3 polydimethylsiloxyethyl dimethicone)
Silicone branched type polyglycerin-modified silicone. Examples of commercially available products include polyglyceryl-3 polydimethylsiloxyethyl dimethicone (trade name: KF-6104) manufactured by Shin-Etsu Chemical Co., Ltd.
In addition to bis- (glyceryl / lauryl) glyceryl lauryl dimethicone and / or polyglyceryl-3 polydimethylsiloxyethyl dimethicone, the addition of surfactants commonly used to prepare water-in-oil emulsified emulsions is restricted. It is not something to do. Examples of the surfactant for such a purpose include PEG-9 polydimethylsiloxyethyl dimethicone, PEG-9 dimethicone, and lauryl PEG-9 polydimethylsiloxyethyl dimethicone.

The water-in-oil emulsified cosmetic of the present invention requires the component (C), bis- (glyceryl / lauryl) glyceryl lauryl dimethicone and / or polyglyceryl-3 polydimethylsiloxyethyl dimethicone, but the sum of both components is essential. It is preferably contained in an amount of 1 to 6% by mass.
Further, when an arbitrary surfactant is blended, it is preferable that the total amount of the component (C) and the arbitrary surfactant is 5 to 8% by mass.

The water-in-oil emulsified cosmetic of the present invention includes other surfactants, powders, oils, higher fatty acids, higher alcohols, silicone-based thickeners, polyhydric alcohols, as long as the effects of the present invention are not impaired. It can contain sugars, sugar alcohols, water-soluble polymers, other thickeners, preservatives, metal ion sequestering agents, ultraviolet absorbers, moisturizers such as hyaluronic acid, fragrances, pH adjusters and the like. In addition, vitamins, skin activators, blood circulation promoters, indigenous bacteria control agents, active oxygen scavengers, anti-inflammatory agents, whitening agents, bactericides and other other medicinal ingredients and physiologically active ingredients can be contained. ..

As other surfactants, nonionic surfactants, anionic surfactants, amphoteric surfactants and the like can be blended.

The powders include iron oxide, gunjo, chromium oxide, hydroxyapatite, silica, talc, kaolin, boron nitride, mica, crystalline cellulose powder, silk powder, alkyl polyacrylate powder, nylon powder, and polyethylene powder. , Polystyrene powder and the like can be exemplified. Further, a surface-treated powder that has been subjected to silicone treatment, fluorine treatment, or the like may be used. Further, a composite powder composed of a plurality of types of insoluble powders may be used. As the insoluble powder, a commercially available dispersion that has been previously dispersed in silicone oil or the like may be used.

As the oil agent, for example, silicone oil, ester oil, fats and oils, and hydrocarbons are preferable. Examples of the silicone oil include dimethicone, methyltrimethicone, caprylylmethicone, phenyltrimethicone, hydrogendimethicone, diphenylsiloxyphenyltrimethicone, cyclohexasiloxane, cyclopentasiloxane, and decamethylcyclopentasiloxane.
Examples of the ester oil include cetyl 2-ethylhexanoate, pentaerythrityl tetraoctanoate, 1,3-butylene glycol diisononanoic acid, 1,3-butylene glycol di2-ethylhexanoic acid, dipropylene glycol diisononanoate, and diisononanoate. 2-ethylhexanoic acid dipropylene glycol, isononyl isononanoate, isotridecyl isononanoate, glyceryl tri-2-ethylhexanoate, capric triglyceride, glyceryl triisostearate, dicaprate neopentyl Le, isostearyl neopentanoate, tetraethyl hexanoate penta Examples include erythricyl and the like.
Examples of the fats and oils include liquid fats and oils such as camellia oil, evening primrose oil, macadamia nut oil, olive oil, rapeseed oil, corn oil, sesame oil, jojoba oil, germ oil, and wheat germ oil.
Examples of hydrocarbons include liquid paraffin, squalene, squalene, microcrystalline wax and the like.

Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, docosahexaenoic acid (DHA), and eicosapentaenoic acid (EPA).

Examples of the higher alcohol include linear alcohols such as lauryl alcohol, stearyl alcohol, cetyl alcohol and cetostearyl alcohol, branched chain alcohols such as monostearyl glycerin ether, lanolin alcohol, cholesterol, phytosterol and octyldodecanol.

Examples of the silicone-based thickener include a partially crosslinked organopolysiloxane, an alkyl-modified partially crosslinked organopolysiloxane, and a silicone branched alkyl-modified partially crosslinked organopolysiloxane. A gel mixture in which a partially crosslinked organopolysiloxane and an oil agent such as cyclopentasiloxane or dimethicone are mixed in advance may be used.

Examples of the water-soluble polymer include arabic rubber, tragacanth gum, galactan, guar gum, carrageenan, pectin, agar, quince seed extract, dextran, purulan, carboxymethyl starch, collagen, casein, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, and hydroxy. Examples thereof include ethyl cellulose, sodium carboxymethyl cellulose, sodium alginate, and carboxyvinyl polymer.

Examples of other thickeners include glyceryl icosanate behenate, dextrin stearate, and dextrin isostearate.

Examples of the preservative include methylparaben and ethylparaben.

Examples of the sequestrant include edetates such as ethylenediaminetetraacetic acid disodium, edetic acid, and edetic sodium salt.

Examples of the ultraviolet absorber include para-aminobenzoic acid, phenyl salicylate, isopropyl paramethoxycinnamic acid, octyl paramethoxycinnamic acid, and 2,4-dihydroxybenzophenone.

Examples of vitamins include vitamin A oil, vitamin A such as retinol, vitamin B6 such as riboflavin, B6 such as pyridoxin hydrochloride, L-ascorbic acid, L-ascorbic acid phosphate ester, and L-ascorbic acid monopalmitin. Acid ester, vitamin Cs such as L-ascorbic acid dipalmitic acid ester, L-ascorbic acid-2-glucoside, pantothenic acids such as calcium pantothenate, vitamin Ds such as vitamin D6 and cholecalciferol, α-tocopherol, Examples of vitamin Es such as tocopherol acetate and DL-α-tocopherol nicotinate can be exemplified.

Examples of suitable products for the water-in-oil emulsified cosmetic of the present invention include sunscreen cosmetics such as sunscreen cream, sunscreen emulsion, suncare spray, and sunscreen mousse. In addition, since it has a high UV protection effect, it may be used as a makeup base with a UV blocking function, a foundation cream, or a milky lotion.

The results of the use test using the compositions of Examples (Table 1) and Comparative Example (Table 2) are shown below, and the present invention will be described in more detail. The compositions of Examples and Comparative Examples have the following characteristics.
The compositions of Examples and Comparative Examples commonly contain 24% by mass of titanium oxide and zinc oxide, which are metal oxides (A), in a total amount. The surfactant contains only one or both of the essential surfactant (C) and any other surfactant.
Example 1 contains 6% by weight in total of the essential surfactant (C) and any other surfactant.
Examples 2 and 3 contain 5.5% by mass of the total amount of the essential surfactant (C) and any other surfactant.
Example 4 has a formulation structure containing only the essential surfactant (C) without containing any surfactant, and the surfactant (C) is blended in an amount of 5.5% by mass.
Then, 6% by mass of (B) di (caprylic acid / capric acid) propanediol is blended in each of Examples 1, 2 and 4 , and 4% by mass of (B) is blended in Example 3. There is.

On the other hand, Comparative Examples 1 to 14 have a composition lacking or not containing either the oil agent (B) or the surfactant (C).
Comparative Examples 1 to 4 did not contain the essential surfactant (C) and contained only any other surfactant, and the blending amounts thereof were 6% by mass in Comparative Example 1 and 5. It is 5% by mass.
Comparative Examples 5 to 9 contain both the essential surfactant (C) and any other surfactant, and the total amount thereof is 5.5% by mass. Further, the di (caprylic acid / capric acid) propanediol of the oil agent (B) is not blended.
Comparative Examples 10 to 14 have a composition that does not contain both the oil agent (B) and the surfactant (C). And each contains only 6% by weight of any other surfactant.
In Comparative Examples 5 to 14, instead of the oil agent (B), any of other oil agents such as isotridecyl isononanoate, squalane, cetyl ethylcaproate, isostearyl neopentate, and dimethicone was blended in an amount of 6% by mass. doing.

1. 1. Preparation of Test Products Water-in-oil emulsified cosmetics having the compositions shown in Tables 1 (Examples 1 to 4) and Table 2 (Comparative Examples 1 to 14) were prepared by the following preparation methods.

2. Preparation method The oily components were mixed at room temperature and mixed with a homomixer (3000 rpm) for 10 minutes. While adding the water-soluble component to the mixture, the mixture was mixed with a homomixer (3000 rpm) and emulsified for 1 to 2 minutes. Mixing was continued for 10 minutes with a homomixer (4500 rpm) to complete the preparation.

3. 3. Evaluation (white floating 1, white floating 2, detergency)
The water-in-oil emulsified cosmetics shown in Tables 1 and 2 were evaluated by a professional sensory evaluator by the following test method. In addition, if there are any special notes regarding usability, we asked them to report.
The results are shown in the lower part of Tables 1 and 2.

<Whitening 1 (transparency when applied)>
0.02 g of the obtained water-in-oil emulsified cosmetic was applied to the inner part of the upper arm, and ² μg was spread per 1 cm 2. Then, the presence or absence of whitening was visually evaluated according to the following criteria.
(Evaluation criteria)
〇: Not white floating ×: White floating

<White floating 2 (transparency when wet)>
30 mg of the water-in-oil emulsified cosmetic obtained on a plate made of polymethyl methacrylate resin (PMMA) was spread over an area of 5 cm × 5 cm and dried. Then it was flooded. After 5 minutes, it was taken out and placed under a black background, and the degree of whitening was visually evaluated according to the following criteria.
(Evaluation criteria)
◎: No whitening 〇: There is some whitening, but it is hardly noticeable ×: There is whitening

<Cleanability (easy to wash off)>
0.02 g of the obtained water-in-oil emulsified cosmetic was weighed, spread over an area of 2 cm × 2 cm on the inner side of the upper arm, and dried for 30 minutes. Subsequently, one push of a commercially available facial cleanser (Moist Body Wash manufactured by FANCL Cosmetics Co., Ltd.) is placed on the applied portion, rubbed with a finger 20 times, and rinsed with running water. After repeating this washing three times, it was lightly pressed with a tissue to remove water, and visually observed and evaluated.
The evaluation criteria were based on the following criteria.
(Evaluation criteria)
○: I felt it was easy to drop ×: I felt it was difficult to drop

4. Evaluation Results and Discussion The water-in-oil dairy cosmetics of Examples 1 to 4 having the constitution of the present invention have a high content of metal oxide of 24% by mass, but whitening occurs when applied to the skin. It was confirmed that there was no whiteness, it did not turn white even when it got wet with water, and it was easy to wash. In addition, all the examples were evaluated to have good elongation at the time of application.
Among them, (C) Example 1 in which bis- (glyceryl / lauryl) glyceryl lauryl dimethicone was blended as a surfactant was particularly excellent in transparency (no whitening) when wet with water, and was visually sensory. The evaluation result was "◎: no whitening", and the cleanability was also evaluated as "○: easy to remove". In addition, there was a special note that when applied to the skin, it spreads particularly well.
Furthermore, it was confirmed that the cosmetics of Examples 1 to 4 were excellent in the UV blocking effect.
On the other hand, in Comparative Examples 1 to 4, there was no whitening when applied to the skin and there was transparency, but when it got wet with water, whitening occurred and the transparency deteriorated. Comparative Examples 1 to 4 were evaluated as "○: easy to remove" in terms of detergency, but as described above, it was a comprehensive evaluation by the sensory evaluator that it was not preferable because whitening occurred when it got wet with water. ..
Comparative Examples 5 to 9 were evaluated to have no whitening and transparency when applied to the skin, and to have good transparency without whitening even when wet with water. However, it was evaluated as "x: difficult to remove" due to poor detergency. Comparative Examples 5 to 9 were also comprehensive evaluations by sensory evaluators who were unfavorable.
In Comparative Examples 10 to 14, the evaluation of detergency was low even though the blending amount of the arbitrary surfactant was as high as 6% by mass. Therefore, it was a comprehensive evaluation by the sensory evaluator, which was unfavorable.

From the results of the sensory evaluation as described above, the water-in-oil dairy cosmetics having the constitution of the present invention spread well despite the high content of metal oxides, and there is no whitening when applied to the skin. It was clarified that it does not turn white even when it gets wet with water, and that it is easy to wash.
Since the water-in-oil emulsified cosmetic of the present invention has the above-mentioned characteristics, it is preferable as a sunscreen cosmetic containing a high amount of metal oxide, a makeup base, a foundation, and the like. be.

Prescription example 1 (sunscreen emulsion)
Ingredient mass%
1. 1. Fine particle titanium oxide 5
2. Fine particle zinc oxide 15
3. 3. Bis- (Glyceryl / Lauryl) Glyceryl Lauryl Dimethicone 1.5
4. Polyglyceryl-3 polydimethylsiloxyethyl dimethicone 1.5
5. PEG-9 Polydimethylsiloxyethyl Dimethicone 2.5
6. Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone 2.5
7. Di (caprylic acid / capric acid) propanediol 8
8. Cyclopentasiloxane residue 9. Dimethicone 5
10. Polyhydroxystearic acid 0.05
11. Water 20
12. Sodium chloride 1
13. Preservatives Appropriate amount (preparation method)
Ingredients 1. -10. Was mixed at room temperature and mixed with a homomixer (3000 rpm) for 10 minutes. Ingredients in the mixture 11. ~ 13. Was mixed with a homomixer (3000 rpm) and emulsified (1 to 2 minutes). Mixing was continued for 10 minutes with a homomixer (4500 rpm) to complete the preparation.
The sunscreen emulsion of Formulation Example 1 spread well and did not appear white at all when applied to the skin. Even when it got wet with water, it did not appear white and had excellent transparency. In addition, it could be easily removed with a washing pigment without removing it with an oil-based cleansing agent.

Claims (4)

(A) a metal oxide, (B) di and a (caprylic acid / capric acid) propanediol 4-8 wt% per cosmetic, (C) the surfactant has 5-8 wt% containing per cosmetic , bi scan - (glyceryl / lauryl) glyceryl lauryl dimethicone and / or polyglyceryl-3 polydimethylsiloxyethyl dimethicone cosmetic per Ri 1-6 wt% including water-in-oil emulsified cosmetic. (A) The water-in-oil emulsified cosmetic according to claim 1, wherein the metal oxide is one or more selected from titanium oxide and zinc oxide. (A) The water-in-oil emulsified cosmetic according to claim 1 or 2, which contains 18 to 30% by mass of a metal oxide. The water-in-oil emulsified cosmetic according to any one of claims 1 to 3, which is used for sunscreens, makeup bases, and foundations.